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Materials Today: Proceedings 3 (2016) 936 941

DAS 2015

GCP and TCP phases presented in nickel-base superalloys

Juraj Belana*
a

University of ilina, Faculty of Mechanical Engineering, Department of Material Engineering, Univerzitn 8215/1, 010 26 ilina, Slovakia

Abstract
The paper gives a short description of intermetallic phases presented in cast and wrought nickel based superalloys. Generally, the
intermetallic phases presented in nickel based superalloys can be divided into three main groups: i - primary and secondary
carbides; ii - GCP (Geometrically Close-Packed); and iii - TCP (Topologically Close-Packed). Of course, mentioned
intermetallic phases have various influences on mechanical properties. Some of them have increasing strength or creep rupture
life as well as fatigue properties. On the other hand, some act negatively to mechanical properties. Its influence strongly depends
from morphology (shape or orientation in matrix), and quantity (e.g. small amount of delta phase Ni 3Nb increases tensile strength
and fatigue properties when situated on grain boundary of wrought IN 718 alloy) as well. Most of phases are presented after
applied heat treatment, which commonly consist of solution annealing followed by artificial ageing.
2015 Elsevier Ltd. All rights reserved.
2016 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the Committee Members of 32nd DANUBIA ADRIA SYMPOSIUM on
Selection and Peer-review under responsibility of the Committee Members of 32nd DANUBIA ADRIA SYMPOSIUM on
AdvancedininExperimental
Experimental
Mechanics
(DAS
2015).
Advanced
Mechanics
(DAS
2015)
Keywords: Intermetallic phases; nickel based superalloys; GCP (Geometrically Close-Packed); TCP (Topologically ClosePacked); micrographs; SEM Scanning Electron Microscopy; mechanical properties; superalloys hardening.

1. Introduction
Nickel- base superalloys are important construction materials used for the most stressed shafts of high-pressure
turbine, exposed to high dynamic stress and various temperatures in dioxide-corrosion condition [1].
Superalloys are available in cast (usually heat treated or otherwise processed) or wrought (often heat treated or
otherwise processed) forms [2].

* Corresponding author. Tel.: +421-41-513-2611; fax: +421-41-565-2940.

E-mail address: juraj.belan@fstroj.uniza.sk

2214-7853 2016 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of the Committee Members of 32nd DANUBIA ADRIA SYMPOSIUM on
Advanced in Experimental Mechanics (DAS 2015)
doi:10.1016/j.matpr.2016.03.024

Juraj Belan / Materials Today: Proceedings 3 (2016) 936 941

937

Wrought alloys are more homogenous than cast alloys, which usually have segregation caused by the
solidification process. Segregation is a natural consequence of solidification of alloys but may be more severe in
some cases than in others. Wrought alloys generally are considered more ductile than cast alloys.
Cast alloys are found in the hot section areas of gas turbines, especially as airfoils, that is, blades and vanes. Most
castings are polycrystalline (PC) equiaxed, but others are directionally solidified (DS). Castings are intrinsically
stronger than forgings at elevated temperature. The coarse grain size of PC castings, as compared to finer-grained
forgings, favours strength at high temperatures.
2. Intermetallic phases
There are three groups of superalloys (iron-nickel, nickel, and cobalt-base), which are further subdivided into cast
and wrought (where wrought includes powder metallurgy processing) macrostructures. Superalloys consist of the
austenitic fcc matrix phase J plus a variety of secondary phases. Secondary phases of value in controlling properties
are the fcc carbides MC, M23C6, M6C, and M7C3 (rare) in virtually all superalloy types; gamma prime (Jc) fcc
ordered Ni3(Al,Ti); gamma double prime (Jcc) bct ordered Ni3Nb; eta (K) hexagonal ordered Ni3Ti; and the delta ()
orthorhombic Ni3Nb intermetallic compounds in nickel- and iron-nickel-base superalloys. The Jc, Jcc, and K phases
also are known as geometrically close-packed (GCP) phases. In addition to grain size and morphology, (plus
occasional cold work) it is the production and control (manipulation) of the various phases that give superalloys
their unique characteristics.
The superalloys derive their strength mostly from solid-solution hardeners and precipitated phases. Principal
strengthening precipitate phases are Jc and Jcc, which are found in iron-nickel- and nickel-base superalloys. Carbides
may provide limited strengthening directly (e.g., through dispersion hardening) or, more commonly, indirectly (e.g.,
by stabilizing grain boundaries against excessive shear). Carbides are found in all three superalloy groups. The and
K phases are useful (along with Jc) in control of structure of wrought iron-nickel- and nickel-base superalloys during
processing. The extent to which they contribute directly to strengthening depends on the alloy and its processing. In
addition to those elements that produce solid solution hardening and/or promote carbide and Jc formation, other
elements (e.g., boron, zirconium, and hafnium) are added to enhance mechanical or chemical properties. These
minor elements are not customarily found in most cobalt-base alloys. Some carbide and Jc - forming elements may
contribute significantly to chemical properties as well. Borides may form in the iron-nickel and nickel-base
superalloys. [3-6].
Detrimental phases also form in the superalloys. Topologically Close-Packed phases (TCP) are those such as
(FeCr, FeCrMo, CrCo), , and Laves (among others) that generally are brittle and detrimental to the mechanical
properties of superalloys, particularly nickel-base superalloys. These phases can form in iron-nickel and cobalt-base
superalloys as well. Based on early studies on stainless steels, these phases, and particularly phase, can be
controlled by adjustments in alloy chemistry. Moreover, these phases are not always detrimental. Much evidence
exists to show that very small amounts of may be beneficial to creep-rupture strength. Table 1 [2] summarizes data
on the commonly encountered phases in iron-nickel- and nickel-base superalloys.
Table 1. Selected GCP and TCP observed in superalloys.
Phase

Crystal Structure

Formula

Comments

Jc

FCC (ordered L12)

Ni3Al(Ti)

Principal strengthening phase in many nickel- and nickel-iron-base superalloys; crystal

lattice varies slightly in size (0 to 0.5%) from that of austenite matrix; shape varies from
spherical to cubic; size varies with exposure time and temperature. Gamma prime is
spherical in iron nickel-base and in some of the older nickel-base alloys. In the more
recently developed nickel-base alloys, Jc is generally cuboidal. Experiments have shown
that variations in molybdenum content and in the aluminium/titanium ratio can change
the morphology of Jc. With increasing J/Jc mismatch, the shape changes in the following
order: spherical, globular, blocky, and cuboidal. When the J/Jc lattice mismatch is high,
extended exposure above 700C causes undesirable K (Ni3Ti) or (Ni3Nb) phases to
form.

Jcc

BCT (ordered D022)

Ni3Nb

Principal strengthening phase in Inconel 718; Jcc precipitates are coherent disk-shaped
particles that form on the {100} planes (avg diam approximately 600 , thickness

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Juraj Belan / Materials Today: Proceedings 3 (2016) 936 941

approximately 50 to 90 ). Bright-field transmission electron microscopy (TEM)
examination is unsatisfactory for resolving Jcc due to the high density of the precipitates
and the strong contrast from the coherency strain field around the precipitates. However,
dark-field TEM examination provides excellent imaging of the Jcc by selective imaging
of precipitates that produce specific superlattice reflections. In addition, Jcc can be
separated from Jc using the dark-field mode, because the Jcc dark-field image is
substantially brighter than that of Jc.

HCP (ordered D024)

Ni3Ti (no
solubility for other
elements)

Found in iron-nickel-, cobalt-, and nickel-base superalloys with high titanium/aluminium

ratios after extended exposure; may form intergranularly in a cellular form or
intragranularly as acicular platelets in a Widmansttten pattern.

Orthorombic

Ni3Nb

Observed in overaged Inconel 718; has an acicular shape when formed between 815 and
980C; forms by cellular reaction at low aging temperatures and by intragranular
precipitation at high aging temperatures.

Tetragonal

FeCr, FeCrMo,
CrCo

Most often observed in iron-nickel- and cobalt base superalloys, less commonly in
nickel-base alloys; appears as irregularly shaped globules, often elongated; forms after
extended exposure between 540 and 980C.

Laves

Hexagonal

Fe2Nb, Co2Ti,
Fe2Ti

Most common in iron-base and cobalt-base superalloys; usually appears as irregularly

shaped globules, often elongated, or as platelets after extended high-temperature
exposure.

Rhombohedral

(Fe, Co)7(Mo, W)6

Generally observed in alloys with high levels of molybdenum or tungsten; appears as

coarse, irregular Widmansttten platelets; forms at high temperatures.

The most important class of nickel base superalloys is that strengthened by intermetallic compound precipitation
in an austenitic fcc matrix. For alloys with titanium and aluminium, the strengthening precipitate is Jc. For niobiumstrengthened nickel-base superalloys, the strengthening precipitate is Jcc. Some nickel-base alloys may contain
niobium plus titanium and/or aluminium and use both Jc and Jcc precipitates in strengthening.
Superalloys contain a variety of elements in a large number of combinations to produce desired effects. Table 2
lists the role of some alloy elements in superalloys.
Table 2. Role of alloying elements in Nickel-base superalloys.
Effect

Elements

Solid solution strengtheners

Co, Cr, Fe, Mo, W, Ta, Re

Carbide form:
MC

W, Ta, Ti, Mo, Nb, Hf

M7C3

Cr

M23C6

Cr, Mo, W

M6C

Mo, W, Nb

Forms Jc Ni3(Al, Ti)

Al, Ti

Raises solvus temperature of Jc

Co

Hardening precipitates and/or intermetallics

Al, Ti, Nb

Oxidation resistance

Al, Cr, Y, La, Ce

Improve hot corrosion resistance

La, Th

Sulfidation resistance

Cr, Co, Si

Improves creep properties

B, Ta

Increases rupture strength

Grain boundary refiners

B, C, Zr, Hf

Retard Jc coarsening

Re

Juraj Belan / Materials Today: Proceedings 3 (2016) 936 941

Some elements go into solid solution to provide one or more of the following: strength (molybdenum, tantalum,
tungsten, and rhenium); oxidation resistance (chromium and aluminium); hot corrosion resistance (titanium); phase
stability (nickel); and increased volume fractions (Vf) of favourable secondary precipitates (cobalt). Other elements
are added to form hardening precipitates such as Jc (aluminium and titanium) and Jcc (niobium). A major addition to
nickel-base superalloy chemistry in recent years has been the element rhenium, which has extended the temperature
capability of the columnar grain directionally solidified (CGDS) and single crystal directionally solidified (SCDS)
casting alloys. Rhenium appears to produce these improvements by significantly reducing the coarsening rate for Jc.
Minor elements (carbon and boron) are added to form carbides and borides; these and other elements (e.g.,
magnesium) are added for purposes of tramp-element control. Some elements (boron, zirconium, and hafnium) also
are added to promote grain-boundary effects other than precipitation or carbide formation. Lanthanum has been
added to some alloys to promote oxidation resistance, and yttrium has been added to coatings to enhance coating
life.
Many elements (cobalt, molybdenum, tungsten, rhenium, chromium, etc.), although added for their favourable
alloying qualities, can participate, in some circumstances, in undesirable TCP phase formation (, , Laves, etc.).
The TCP phases usually have low ductility (are brittle) and cause loss of mechanical (and sometimes corrosion)
properties when present in anything more than trace amounts.

3. Microstructures in Ni-base superalloys

Typical operating microstructures of representative superalloys are shown in Fig. 1. Microstructures are shown
for a polycrystalline (PC) cast and wrought nickel superalloys and indicate the carbide phases that are usually seen.
At higher magnifications, cuboidal Jc is visible in both wrought and cast nickel-base superalloys, as are grain
boundaries decorated with phases (mostly carbides). In the cast nickel-base superalloys at moderate magnification,
eutectic J/Jc nodules may be found. These modules are really a J/Jc eutectic solidification product.

a)

b)

c)

d)

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Juraj Belan / Materials Today: Proceedings 3 (2016) 936 941

e)

f)

Fig. 1 A typical SEM microstructures of nickel base superalloys: a) wrought EI 929; b) cast S6K with carbides situated on grain-boundary (a)
or in interdendritic areas of cast alloy (b) most of them in script morphology primary carbides MC; c) Jc in wrought IN 718 alloy together with
Ni3Nb needle like morphology, Jcc not visible, but present; d) Jc in cast S6K alloy with obvious J/Jc eutectics typical for cast nickel base
superalloy; e) primary carbide detail presented in script or skeleton form; f) detail of J/Jc eutectic in S6K type alloy after applied re-heating at
800C/ 10 hrs. and water cooled.

TCP phases are very detrimental because of two main factors. At first, when they nucleate and grow, they deplete
the J-matrix phase from solid solution strengtheners. This leads to decreased creep resistance of the material [7, 8].
Further, TCP phases are brittle and exhibit a complex lath- or plate-like morphology [9], which evolves with time
[10]. Thus, cracks are easily nucleated. As a consequence the fatigue life-time and tensile ductility of the material
will be decreased [8]. It is widely accepted that precipitation of TCP phases can be suppressed by an addition of
ruthenium. Several possible mechanisms for this effect were proposed based on experiments [7, 1114] and
simulations [15, 16].
However, TCP phases are not only the one, which are forming during high temperature operation of alloys.
Especially when the alloys are protected from high temperature effect with protective layers such as layers based on
aluminium or aluminium and silicon mixture a E phase (NiAl) is forming also very often. This E phase is the
reason of protective layer degradation and is presented as columnar shape morphology in underlayer area, Fig. 2.
Because of Ni and Al elements diffusion is mentioned E phase dissolving into Jc - phase (Ni3Al) and Al2O3 oxide
with following dissolving Jc - phase into Al2O3. This is the way in which the protective layer is losing its heatproof
properties.

a)

b)

Fig. 2 Other intermetallic phases formation in Ni-base superalloys: a) the phase formation in interdendritic area of S6K alloy type; b) the E
phase columnar shape morphology in underlayer area IN 713LC alloy type, SEM.

Juraj Belan / Materials Today: Proceedings 3 (2016) 936 941

4. Summary
The major phases and form of occurrence in nickel-base alloys are:
J matrix, in which the continuous matrix is an fcc nickel-base nonmagnetic phase that usually contains a high
percentage of solid-solution elements such as cobalt, iron, chromium, molybdenum, and tungsten. All nickel-base
alloys contain this phase as the matrix.
Jc formed from aluminium and titanium, which react with nickel to precipitate a phase coherent with the
austenitic gamma matrix. Other elements, notably niobium, tantalum, and chromium, also enter Jc. This is the
principal high-temperature strengthening phase. It appears as spheres or cuboids when properly formed.
Jcc in which nickel and niobium combine in the presence of iron to form bct Ni3Nb, which is coherent with the
gamma matrix, while inducing large mismatch strains (of the order of 2.9%). This phase provides very high strength
at low-to-intermediate temperatures, but it is unstable at temperatures above about 649C. This precipitate is found
in only a few nickel-(nickel-iron-) base alloys.
Carbides, where carbon in amounts of about 0.02 to 0.2 wt% combines with reactive elements, such as titanium,
tantalum, hafnium, and niobium, to form metal carbides. There are several carbide phases. During heat treatment
and service, MC carbides tend to decompose and generate other carbides, such as M23C6 and/or M6C, which tend to
form at grain boundaries. Carbides in nominal solid-solution alloys may form after extended service exposures.
TCP phases, which are usually platelike or needlelike phases such as and Laves that may form for some
compositions and under certain conditions. These phases can cause lowered rupture strength and ductility. The
likelihood of their presence increases as the solute segregation of the ingot increases.
Acknowledgements
This work has been supported by Scientific Grant Agency of Ministry of Education of Slovak Republic
No1/0533/15, No 044U-4/2014 and project EU ITMS 26110230117.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

R., J., E., Glenny, High Temperature Materials in Gas Turbines, Elsevier, Amsterdam, 1974.
M., J., Donachie, S., J., Donachie, Superalloys A technical guide, 2nd ed. ASM International, USA, 2002.
M., Durand-Chare, The Microstructure of Superalloys, Gordon & Breach Science Publishers, Amsterdam, 1997.
H., Chandler et al., Heat Treater's Guide, Practices and Procedures for Nonferrous Alloys, ASM International, USA, 2006.
J., R., Davis, ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys, 1st edition, ASM International, Ohio, 2000.
R., Cozar, A., Pineau, Metall. Trans., vol. 4, 1973, 47-59.
R.A. Hobbs, L. Zhang, C.M.F. Rae, S. Tin, Mechanisms of topologically close-packed phase suppression in an experimental rutheniumbearing single-crystal nickel-base superalloy at 1100 C, Metall. Mater. Trans. A 39A (2008) 10141025.
[8] M. Simonetti, P. Caron, Role and behavior of l phase during deformation of a nickel-based single crystal superalloy, Mater. Sci. Eng. A
A254 (1998) 112.
[9] K. Matuszewski, R. Rettig, M. Rasin ski, K.J. Kurzydowski, R.F. Singer, The three-dimensional morphology of topologically close packed
phases in a high rhenium containing nickel based superalloy, Adv. Eng. Mater. 16 (2014) 171175.
[10] K. Matuszewski, R. Rettig, R.F. Singer, The effect of Ru on precipitation of topologically close packed phases in Re-containing Ni base
superalloys: Quantitative FIB-SEM investigation and 3D image modeling, in: J. Guedou, J. Chonne (Eds.), Proceedings of 2nd European
Symposium on Superalloys and their Applications (Eurosuperalloys 2014), MATEC Web of conferences, 14 (2014), 129134.
[11] A. Sato, H. Harada, T. Yokokawa, T. Murakumo, Y. Koizumi, T. Kobayashi, The effects of ruthenium on the phase stability of fourth
generation Ni-base single crystal superalloys, Scripta Mater. 54 (2006) 16791684.
[12] K.S. OHara, W.S. Walston, E.W. Ross, R. Darolia, United States Patent 5482789, January 9, 1996.
[13] S. Neumeier, F. Pyczak, M. Gken, The influence of ruthenium and rhenium on the local properties of the gamma- and gamma prime-phase
in nickel-base superalloys and their consequences for alloy behavior, in: R.C. Reed, K.A. Green, P. Caron, T.P. Gabb, M.G. Fahrmann, E.S.
Huron, S.A. Woodard (Eds.), Superalloys 2008, Metals and Materials Society, Seven Springs, The Minerals, 2008, pp. 109119.
[14] F. Pyczak, S. Neumeier, M. Gken, Temperature dependence of element partitioning in rhenium and ruthenium bearing nickel-base
superalloys, Mater. Sci. Eng. A A527 (2010) 79397943.
[15] R. Rettig, R.F. Singer, Influence of ruthenium on topologically close packed phase precipitation in single-crystal Ni-based superalloys:
numerical experiments and validation, in: E.S. Huron, R.C. Reed, M.C. Hardy, M.J. Mills, R.E. Montero, P.D. Portella, J. Telesman (Eds.),
Superalloys 2012, Metals and Materials Society, Seven Springs, The Minerals, 2012, pp. 205214.
[16] R. Rettig, A. Heckl, R.F. Singer, Modeling of precipitation kinetics of TCP-phases in single crystal nickel-base superalloys, Adv. Mater. Res.
278 (2011) 180185.

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